EP1427764A1 - Hydrocarbon resins from aryl norbornene derivatives - Google Patents
Hydrocarbon resins from aryl norbornene derivativesInfo
- Publication number
- EP1427764A1 EP1427764A1 EP02766258A EP02766258A EP1427764A1 EP 1427764 A1 EP1427764 A1 EP 1427764A1 EP 02766258 A EP02766258 A EP 02766258A EP 02766258 A EP02766258 A EP 02766258A EP 1427764 A1 EP1427764 A1 EP 1427764A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ranging
- aryl
- phenyl
- group
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- -1 aryl norbornene derivatives Chemical class 0.000 title claims abstract description 46
- 239000013032 Hydrocarbon resin Substances 0.000 title abstract description 15
- 229920006270 hydrocarbon resin Polymers 0.000 title abstract description 15
- 229920001519 homopolymer Polymers 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 22
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 15
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims description 63
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 16
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 10
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 9
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical class 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 5
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 42
- 239000011347 resin Substances 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VPTUWWMMOXQJHX-UHFFFAOYSA-N C1C2CCC1=C1C2CCC1 Chemical compound C1C2CCC1=C1C2CCC1 VPTUWWMMOXQJHX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical class C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 235000015096 spirit Nutrition 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 3
- ARPPLBPJWJEDIJ-UHFFFAOYSA-N aniline;methylcyclohexane Chemical compound CC1CCCCC1.NC1=CC=CC=C1 ARPPLBPJWJEDIJ-UHFFFAOYSA-N 0.000 description 3
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 150000002848 norbornenes Chemical class 0.000 description 3
- LKWKIVHUCKVYOA-UHFFFAOYSA-N phosphoric acid;trifluoroborane Chemical compound FB(F)F.OP(O)(O)=O LKWKIVHUCKVYOA-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- SFFFIHNOEGSAIH-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene;ethene Chemical group C=C.C1C2CCC1C=C2 SFFFIHNOEGSAIH-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 102200145452 rs121908580 Human genes 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Definitions
- This invention relates to novel mixed aliphatic/aromatic hydrocarbon resins, particularly useful for tackifying purposes Also, this invention relates to a novel process for preparing the hyrdrocarbon resins wherein 5- aryl-2-norbornene is polymerized, optionally with other alkenes, in the presence of a Friedel-Crafts catalyst Products resulting from hydrogenation of the hydrocarbon resins are also included within the invention
- norbornene, and derivatives thereof as monomers and comonomers in preparing polymeric materials
- norbornene, and derivatives thereof can be polymerized by ring opening metathesis polymerization method (ROMP), or by catalysis method using metallocene or Ziegler-Natta catalysts
- ROMP ring opening metathesis polymerization method
- Polymers prepared by the ROMP method have unsaturated backbones, and the process involves opening of the strained, unsaturated and bridged 5-member ring of norbornene
- Polymers prepared using Ziegler-Natta catalysts are addition polymers that preserve the norbornene structure
- Ziegler-Natta catalysts are typically based on titanium compounds, in combination with an organoaluminum co- catalyst such as t ⁇ ethylaluminum
- Copolymers of norbornene, or substituted norbornene, with ethylene are commercially available, and are primarily used for optical applications such as compact discs
- a problem associated with norbornene-ethylene copolymers is that the copolymers are brittle below the glass transition temperature of the copolymers. It is known that the use of 5-aryl- substituted norbornene, such as 5-phenyl-2-norbornene overcomes the problem of b ttleness associated with use of norbornene.
- aryl-substituted norbornene such as 5-phenyl-2-norbornene
- metathesis catalysts such as tungsten halides or metallocene catalysts such as zirconocene, with other cyclic alkenes or ethylene, to provide interpolymers that exhibit satisfactory modulus, optical, impact-resistant and strength properties.
- the polymeric products that are known and commercially available are generally high molecular weight polymers, having a M n molecular weight exceeding 4000, and as such, are not suitable for use as tackifiers. It is generally acknowledged that tackifying resins have number average molecular weights (M n ) in the range of about 100 to about 1500.
- the present invention relates to certain mixed aliphatic/aromatic hydrocarbon resins, that are particularly suitable for use as tackifiers.
- the hydrocarbon resins are homopolymers of 5-aryl-2-norbomene, or interpolymers of 5-aryl-2-norbornene with at least one, or more, other cyclic or acyclic alkene.
- the aryl group of the 5-aryl-2-norbomene is any aromatic group or substituent having at least 5 carbon atoms preferably from 5 to about 20 carbon atoms.
- Exemplary aromatic groups or substituents include phenyl, substituted phenyl, indenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl, n-butylphenyl, t methylphenyl, t-butylphenyl, substituted indenyl, substituted naphthyl, and the like.
- novel hydrocarbon resins are characterized by having, in combination, (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (M n ) ranging from about 120 to about 1000, (c) a weight average molecular weight (M w ) ranging from about 150 to about 2000, (d) a z-average molecular weight (M z ) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen determined by 1 H NMR.
- novel 5-aryl-2-norbornene homopolymers and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene may be hydrogenated to produce novel hydrogenated hydrocarbon resins.
- the hydrogenated resins have all the above-recited characteristics, (a) through (e), of the 5-aryl-2-norbornene homopolymers and interpolymers described above, and are further characterized by having (f) a mixed methylcyclohexane aniline cloud point (MMAP) ranging from about 15°C to about 65°C.
- MMAP mixed methylcyclohexane aniline cloud point
- the homopolymers of 5-aryl-2 norbornene, and the interpolymers thereof, with at least one, or more, other cyclic or acyclic alkene, and the resins resulting from the hydrogenation of the homopolymers and interpolymers of the 5-aryl-2-norbornene, are useful as tackifiers for non- woven, hot-melt and pressure sensitive adhesive formulations.
- the novel process of the invention for producing the novel homopolymers of 5-aryl-2-norbornene, and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene(s), described herein, is comprised as follows.
- a 5-aryl-2-norbornene, with a cyclic or acyclic alkene where an interpolymer is desired, is polymerized in the presence of a Friedel-Crafts catalyst, such as, for example, aluminum chloride and boron trifluoride, under suitable polymerization conditions.
- a Friedel-Crafts catalyst such as, for example, aluminum chloride and boron trifluoride
- the present invention relates to certain mixed aliphatic/aromatic hydrocarbon resins, that are particularly suitable for use as tackifiers.
- the hydrocarbon resins are homopolymers of 5-aryl-2-norbornene, or interpolymers of 5-aryl-2-norbornene with at least one, or more, other cyclic or acyclic alkene.
- the aryl group of the 5-aryl-2-norbornene is any aromatic group or substituent having at least 5 carbon atoms preferably from 5 to about 20 carbon atoms.
- Exemplary aromatic groups or substituents include phenyl, substituted phenyl, indenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl, n-butylphenyl, trimethylphenyl, t-butylphenyl, substituted indenyl, substituted naphthyl, and the like.
- novel hydrocarbon resins are characterized by having, in combination, (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (M n ) ranging from about 120 to about 1000, (c) a weight average molecular weight (M w ) ranging from about 150 to about 2000, (d) a z-average molecular weight (M z ) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen determined by 1 H NMR.
- novel 5-aryl-2-norbomene homopolymers and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene may be hydrogenated to produce novel hydrogenated hydrocarbon resins.
- the hydrogenated resins have all the above-recited characteristics, (a) through (e), of the 5-aryl-2-norbomene homopolymers and interpolymers described above, and are further characterized by having (f) a mixed methylcyclohexane aniline cloud point (MMAP) ranging from about 15°C to about 65°C.
- MMAP mixed methylcyclohexane aniline cloud point
- the homopolymers of 5-aryl-2 norbornene, and the interpolymers thereof, with at least one, or more, other cyclic or acyclic alkene, and the resins resulting from the hydrogenation of the homopolymers and interpolymers of the 5-aryl-2-norbomene, are useful as tackifiers for non- woven, hot-melt and pressure sensitive adhesive formulations.
- the novel process of the invention for producing the novel homopolymers of 5-aryl-2-norbornene, and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene(s), described herein, is comprised as follows.
- a 5-aryl-2-norbornene, with a cyclic or acyclic alkene where an interpolymer is desired, is polymerized in the presence of a Friedel-Crafts catalyst, such as, for example, aluminum chloride and boron trifluoride, under suitable polymerization conditions.
- a Friedel-Crafts catalyst such as, for example, aluminum chloride and boron trifluoride
- the polymerization process may be operated either in a continuous manner, or, in a batch manner, utilizing a nitrogen-flushed, oven-dried round bottom flask equipped with an overhead stirrer and an additional funnel.
- the flask is charged with the 5-aryl- 2-norbornene, and, optionally, the at least one, or more, other cyclic or acyclic alkene, and the desired Friedel-Crafts catalyst to form a mixture.
- the resultant mixture is stirred and heated at a temperature of at least 50°C, for a time sufficient to effect the polymerization reaction.
- the temperature in the polymerization process ranges from at least 50°C to about 200°C, and, preferably, ranges from about 80 to about 140°C.
- the reaction time required for the polymerization process ranges from about one hour to about twenty hours, with a reaction time of about two to about six hours preferred. The reaction time is dependent on type of catalyst used, concentration of catalyst used, and other reaction conditions.
- the at least one, or more, other alkene, that may be interpolymerized with the 5-aryl-2-norbornene, to provide the novel hydrocarbon resins may be any cyclic or acyclic alkene having from about 3 to about 20 carbon atoms.
- Suitable cyclic or acyclic alkenes are cyclopentene, dicyclopentadiene, 1 ,5-dicyclooctadiene, 3a,4,7,7a- tetrahydro-4,7-methanoindan (THMINA), 5,6-dihydrodicyclopentadiene, pentenes, piperylene, styrene, alpha-methylstyrene, indene, vinyltoluene, and the like.
- any Friedel-Crafts catalyst is well known to be a catalyst that is capable of.
- Friedel-Crafts catalysts include any metal halide, such as aluminum chloride, aluminum chloride complex with hydrochloric acid, aluminum bromide, aluminum fluoride, zinc chloride, titanium chloride, tin chloride, and the like; any boron halide such as boron trifluoride ether complex, boron trifluoride phosphoric acid complex, boron trichloride, and the like; any strong acid such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, and the like.
- metal halide such as aluminum chloride, aluminum chloride complex with hydrochloric acid, aluminum bromide, aluminum fluoride, zinc chloride, titanium chloride, tin chloride, and the like
- any boron halide such as boron trifluoride ether complex, boron trifluoride phosphoric acid complex, boron trichloride, and the like
- any strong acid such as sulfuric acid, phosphoric acid, hydrochloric
- Friedel-Crafts catalysts preferred for use herein include anhydrous aluminum chloride, boron trifluoride ether complex, and the complex of boron trifluoride with phosphoric acid.
- the amount of Friedel-Crafts catalyst utilized in the polymerization process ranges from about 0.01 % to about 20% by weight of the monomer content of the polymerization process, depending upon the temperature of the reaction, and other reaction conditions.
- the amount of Friedel- Crafts catalyst used in the polymerization process ranges from about 0.1 to about 5% by weight of the monomer content.
- Gardner Color Gardner color of molten resin was measured in accordance with ASTM-D-1544.
- Metier Softening Point the Metier softening point was measured in accordance with ASTM-D-6090-97
- MMAP is the mixed methylcyclohexane aniline cloud point, that is determined in accordance with ASTM D 2500 (1991 ) modified as follows Methylcyclohexane is substituted for the heptane, there is used resm/aniline/methylcyclohexane in a ratio of 1/2/1 (5 g/10 ml/5 ml), and the cloud point is determined by cooling a heated, clear blend of the resin, aniline and methylcyclohexane until complete turbidity occurs DACP is the diacetone cloud point and is determined by cooling a heated homogeneous solution of 5 g resin, 5 g xylene and 5 g of diacetone alcohol to the temperature where the solution becomes cloudy
- M n means number average molecular weight
- M w means weight average molecular weight
- M z means the higher moment of the higher molecular weight distribution based on the mathematical definition
- n is the number of molecules of molecular weight M
- the column is calibrated using polystyrene standards with peak molecular weights ranging from 162 to 19600.
- 35+/-1 mg of sample is dissolved in 20 mL of THF solvent. Aliquots of about 1.5 mL of each standard solution are loaded into the autosampler for analysis according to the run conditions shown above.
- the calibration is calculated using the Universal Calibration method. Molecular weight (M n , M w and M z ) are obtained from the Universal Calibration curve.
- Aromatic Hydrogen Content is defined as the ratio of integration area of aromatic hydrogen relative to the total integration area of hydrogen on the resin's proton nuclear magnetic resonance ( 1 H NMR) spectrum.
- 1 H NMR analyses of the resins in this invention were performed using a JEOL 400 MHz Eclipse ⁇ NMR system with a pulse interval of 10 seconds, acquisition time of 2.7 seconds, pulse angle of 45°, X resolution of 0.37 Hz and number of scans of 200.
- the resin NMR samples are prepared by dissolving known amounts of resins into a carbon tetrachloride solvent containing 0.1 % V/V 1 ,4-dioxane as an internal standard.
- the carbon tetrachloride and 1 ,4-dioxane solvents are reagent grade and available from Aldrich Company.
- the aromatic and olefinic peak areas at approximately 7 ppm and at approximately 5.2 ppm, respectively, are integrated relative to the dioxane peak area at 3.53 ppm for comparative analysis.
- the organic layer was separated from the mixture, dried, filtered and the volatile components were removed by heating under vacuum (10 mmHg) until the base temperature reached 271 °C.
- the yield of the resin was about 76%.
- the molten resin displayed a 13 color on the Gardner scale (neat) and a softening point of 70°C.
- a 1 H NMR analysis showed that this resin had 33% of aromatic hydrogens (calculated theoretical value was 35.7%).
- the homopolymer of the 5-phenyl-2-norbornene had a number average molecular weight (M n ) of 150, a weight average molecular weight (M w ) of 170, and a z-average molecular weight (M z ) of 190.
- the organic layer was separated from the mixture, dried, filtered and the volatile components were removed by heating under vacuum (10 mmHg) until the base temperature reached 271 °C.
- the yield of the resin was 66%.
- the molten resin displayed a 15 color on the Gardner scale (neat) and a softening point of 95°C.
- a 1 H NMR analysis showed that this resin had 33.1 % of aromatic hydrogens (calculated theoretical value was 35.7%).
- the homopolymer of the 5-phenyl-2-norbornene had a number average molecular weight (M n ) of 190, a weight average molecular weight (M w ) of 450, and a z-average molecular weight (M z ) of 1590.
- the reaction was allowed to proceed for an additional 3.5 hours.
- the mixture was worked up by diluting with 100 mL of toluene and 200 mL of mineral spirits. When the temperature dropped below 100°C, about 100 mL of 10% aqueous NaOH solution was added to neutralize the catalyst. The organic layer was separated from the mixture, dried, filtered and the volatile components were stripped under vacuum (20 mmHg) until the base temperature reached 290°C. The yield of the resin was about 81 %. The resin displayed an 18 color on the Gardner scale (neat) and a softening point of 99°C. H NMR analysis showed that this resin had 23% of aromatic hydrogens.
- the interpolymer of 5-phenyl-2-norbomene, styrene and THMINA had a number average molecular weight (M Cincinnati) of 340, a weight average molecular weight (M w ) of 860, and a z-average molecular weight (M z ) of 3200.
- Examples 5 and 6 In the following Examples 5 and 6, there is described the preparation of novel hydrogenated hydrocarbon resins.
- the novel hydrogenated hydrocarbon resins were prepared by hydrogenating the novel homopolymer of 5-phenyl-2-norbomene of Example 2, and by hydrogenating the novel interpolymer comprising 5-phenyl-2-norbornene, styrene and THMINA, of Example 4.
- the 5-phenyl-2-norbomene homopolymer of Example 2 was used herein (referred to as resin) 500 g of a solution of the resin (in xylenes,
- Example 6 there is described the preparation of a novel hydrogenated interpolymer comprised of 50% 5-phenyl-2-norbomene, 20% styrene and 30% THMINA, the resin produced in Example 4 (referred to as resin herein)
- the 5-aryl-2-norbornene homopolymers and interpolymers of this invention, and the hydrogenated 5-aryl-2-norbomene homopolymers and interpolymers of this invention have good properties with regard to compatibility and solubility and can be used effectively as tackifying resins in coatings and adhesives formulations including, but not limited to, non- woven, SBS, acrylics, SIS, and many other applications.
- the resins can also be used in sealants, paints, labels, tapes, modifiers, extenders and processing aids for plastics, printing inks, overprint varnishes and other clear coatings, textile dry sizes, ceramic tile grout, varnishes, waterproofing compositions and wax compounds.
- Example 2 In a manner similar to Example 1 there are prepared homopolymers of 3-methyl-phenyl-2-norbomene and 4-methyl-phenyl-2-norbomene.
- Example 4 In a manner similar to Example 4, there is prepared an interpolymer of 5-phenyl-2-norbomene with 1 ,5-cyclooctadiene.
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Abstract
There are disclosed novel homopolymers of 5-aryl-2-norbornene, and novel interpolymers of 5-aryl-2-norbornene with at least one other cyclic or acyclic alkene, and hydrogenated hydrocarbon resins resulting from hydrogenation of the homopolymers and interpolymers. The products are particularly useful as tackifiers. Also disclosed is a novel process for preparing the homopolymers and interpolymers of the 5-aryl-2-norbornene, wherein there is used as the polymerization catalyst, a Friedel-Crafts catalyst, such as aluminum chloride or boron trifluoride.
Description
HYDROCARBON RESINS FROM ARYL NORBORNENE DERIVATIVES
FIELD OF THE INVENTION
This invention relates to novel mixed aliphatic/aromatic hydrocarbon resins, particularly useful for tackifying purposes Also, this invention relates to a novel process for preparing the hyrdrocarbon resins wherein 5- aryl-2-norbornene is polymerized, optionally with other alkenes, in the presence of a Friedel-Crafts catalyst Products resulting from hydrogenation of the hydrocarbon resins are also included within the invention
BACKGROUND OF THE INVENTION Polymers produced from norbomene derivatives are well known in the art, and there are many processes known for the preparation of the polymers Also known is the use of norbornene, and derivatives thereof, as monomers and comonomers in preparing polymeric materials In general, norbornene, and derivatives thereof, can be polymerized by ring opening metathesis polymerization method (ROMP), or by catalysis method using metallocene or Ziegler-Natta catalysts Polymers prepared by the ROMP method have unsaturated backbones, and the process involves opening of the strained, unsaturated and bridged 5-member ring of norbornene Polymers prepared using Ziegler-Natta catalysts are addition polymers that preserve the norbornene structure Ziegler-Natta catalysts are typically based on titanium compounds, in combination with an organoaluminum co- catalyst such as tπethylaluminum
Copolymers of norbornene, or substituted norbornene, with ethylene, are commercially available, and are primarily used for optical applications such as compact discs A problem associated with norbornene-ethylene copolymers is that the copolymers are brittle below the glass transition
temperature of the copolymers. It is known that the use of 5-aryl- substituted norbornene, such as 5-phenyl-2-norbornene overcomes the problem of b ttleness associated with use of norbornene. It is also known that aryl-substituted norbornene, such as 5-phenyl-2-norbornene, can be copolymerized, using either metathesis catalysts such as tungsten halides or metallocene catalysts such as zirconocene, with other cyclic alkenes or ethylene, to provide interpolymers that exhibit satisfactory modulus, optical, impact-resistant and strength properties.
The polymeric products that are known and commercially available are generally high molecular weight polymers, having a Mn molecular weight exceeding 4000, and as such, are not suitable for use as tackifiers. It is generally acknowledged that tackifying resins have number average molecular weights (Mn) in the range of about 100 to about 1500.
SUMMARY OF THE INVENTION The present invention relates to certain mixed aliphatic/aromatic hydrocarbon resins, that are particularly suitable for use as tackifiers. The hydrocarbon resins are homopolymers of 5-aryl-2-norbomene, or interpolymers of 5-aryl-2-norbornene with at least one, or more, other cyclic or acyclic alkene. The aryl group of the 5-aryl-2-norbomene is any aromatic group or substituent having at least 5 carbon atoms preferably from 5 to about 20 carbon atoms. Exemplary aromatic groups or substituents include phenyl, substituted phenyl, indenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl, n-butylphenyl, t methylphenyl, t-butylphenyl, substituted indenyl, substituted naphthyl, and the like. The novel hydrocarbon resins are characterized by having, in combination, (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about
2000, (d) a z-average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen determined by 1H NMR.
The novel 5-aryl-2-norbornene homopolymers and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene, may be hydrogenated to produce novel hydrogenated hydrocarbon resins. The hydrogenated resins have all the above-recited characteristics, (a) through (e), of the 5-aryl-2-norbornene homopolymers and interpolymers described above, and are further characterized by having (f) a mixed methylcyclohexane aniline cloud point (MMAP) ranging from about 15°C to about 65°C.
The homopolymers of 5-aryl-2 norbornene, and the interpolymers thereof, with at least one, or more, other cyclic or acyclic alkene, and the resins resulting from the hydrogenation of the homopolymers and interpolymers of the 5-aryl-2-norbornene, are useful as tackifiers for non- woven, hot-melt and pressure sensitive adhesive formulations.
The novel process of the invention for producing the novel homopolymers of 5-aryl-2-norbornene, and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene(s), described herein, is comprised as follows. A 5-aryl-2-norbornene, with a cyclic or acyclic alkene where an interpolymer is desired, is polymerized in the presence of a Friedel-Crafts catalyst, such as, for example, aluminum chloride and boron trifluoride, under suitable polymerization conditions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to certain mixed aliphatic/aromatic hydrocarbon resins, that are particularly suitable for use as tackifiers. The hydrocarbon resins are homopolymers of 5-aryl-2-norbornene, or interpolymers of 5-aryl-2-norbornene with at least one, or more, other cyclic or acyclic alkene. The aryl group of the 5-aryl-2-norbornene is any aromatic
group or substituent having at least 5 carbon atoms preferably from 5 to about 20 carbon atoms. Exemplary aromatic groups or substituents include phenyl, substituted phenyl, indenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl, n-butylphenyl, trimethylphenyl, t-butylphenyl, substituted indenyl, substituted naphthyl, and the like. The novel hydrocarbon resins are characterized by having, in combination, (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z-average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen determined by 1H NMR.
The novel 5-aryl-2-norbomene homopolymers and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene, may be hydrogenated to produce novel hydrogenated hydrocarbon resins. The hydrogenated resins have all the above-recited characteristics, (a) through (e), of the 5-aryl-2-norbomene homopolymers and interpolymers described above, and are further characterized by having (f) a mixed methylcyclohexane aniline cloud point (MMAP) ranging from about 15°C to about 65°C.
The homopolymers of 5-aryl-2 norbornene, and the interpolymers thereof, with at least one, or more, other cyclic or acyclic alkene, and the resins resulting from the hydrogenation of the homopolymers and interpolymers of the 5-aryl-2-norbomene, are useful as tackifiers for non- woven, hot-melt and pressure sensitive adhesive formulations.
The novel process of the invention for producing the novel homopolymers of 5-aryl-2-norbornene, and interpolymers thereof with at least one, or more, other cyclic or acyclic alkene(s), described herein, is comprised as follows. A 5-aryl-2-norbornene, with a cyclic or acyclic alkene where an interpolymer is desired, is polymerized in the presence of a
Friedel-Crafts catalyst, such as, for example, aluminum chloride and boron trifluoride, under suitable polymerization conditions.
In further detail, the polymerization process may be operated either in a continuous manner, or, in a batch manner, utilizing a nitrogen-flushed, oven-dried round bottom flask equipped with an overhead stirrer and an additional funnel. In the batch process, the flask is charged with the 5-aryl- 2-norbornene, and, optionally, the at least one, or more, other cyclic or acyclic alkene, and the desired Friedel-Crafts catalyst to form a mixture. The resultant mixture is stirred and heated at a temperature of at least 50°C, for a time sufficient to effect the polymerization reaction. The temperature in the polymerization process ranges from at least 50°C to about 200°C, and, preferably, ranges from about 80 to about 140°C. The reaction time required for the polymerization process ranges from about one hour to about twenty hours, with a reaction time of about two to about six hours preferred. The reaction time is dependent on type of catalyst used, concentration of catalyst used, and other reaction conditions.
The at least one, or more, other alkene, that may be interpolymerized with the 5-aryl-2-norbornene, to provide the novel hydrocarbon resins, may be any cyclic or acyclic alkene having from about 3 to about 20 carbon atoms. Exemplary of suitable cyclic or acyclic alkenes are cyclopentene, dicyclopentadiene, 1 ,5-dicyclooctadiene, 3a,4,7,7a- tetrahydro-4,7-methanoindan (THMINA), 5,6-dihydrodicyclopentadiene, pentenes, piperylene, styrene, alpha-methylstyrene, indene, vinyltoluene, and the like. In the polymerization process of the present invention there is used as the catalyst, any Friedel-Crafts catalyst. A Friedel-Crafts catalyst is well known to be a catalyst that is capable of. catalyzing Friedel-Crafts alkylation/acylation reactions, which are the substitution reactions of hydrogens on an aromatic ring by alkyl groups or acyl groups. Exemplary Friedel-Crafts catalysts include any metal halide, such as aluminum
chloride, aluminum chloride complex with hydrochloric acid, aluminum bromide, aluminum fluoride, zinc chloride, titanium chloride, tin chloride, and the like; any boron halide such as boron trifluoride ether complex, boron trifluoride phosphoric acid complex, boron trichloride, and the like; any strong acid such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, and the like. Friedel-Crafts catalysts preferred for use herein include anhydrous aluminum chloride, boron trifluoride ether complex, and the complex of boron trifluoride with phosphoric acid. The amount of Friedel-Crafts catalyst utilized in the polymerization process ranges from about 0.01 % to about 20% by weight of the monomer content of the polymerization process, depending upon the temperature of the reaction, and other reaction conditions. Preferably, the amount of Friedel- Crafts catalyst used in the polymerization process ranges from about 0.1 to about 5% by weight of the monomer content. The invention will be more readily understood by reference to the following examples. There are, of course, many other forms of this invention which will become obvious to one skilled in the art, once the invention has been fully disclosed, and it will accordingly be recognized that these examples are given for the purpose of illustration only, and are not to be construed as limiting the scope of this invention in any way.
EXAMPLES In the following examples the test procedures listed below were used in evaluating the properties of the 5-aryl-2-norbornene homopolymers and the interpolymers of the 5-aryl-2-norbomene with the at least one, or more, cyclic or acyclic alkenes herein.
Gardner Color — Gardner color of molten resin was measured in accordance with ASTM-D-1544.
Metier Softening Point — the Metier softening point was measured in accordance with ASTM-D-6090-97
Cloud Point — MMAP is the mixed methylcyclohexane aniline cloud point, that is determined in accordance with ASTM D 2500 (1991 ) modified as follows Methylcyclohexane is substituted for the heptane, there is used resm/aniline/methylcyclohexane in a ratio of 1/2/1 (5 g/10 ml/5 ml), and the cloud point is determined by cooling a heated, clear blend of the resin, aniline and methylcyclohexane until complete turbidity occurs DACP is the diacetone cloud point and is determined by cooling a heated homogeneous solution of 5 g resin, 5 g xylene and 5 g of diacetone alcohol to the temperature where the solution becomes cloudy
Molecular Weight
Mn means number average molecular weight Mw means weight average molecular weight
Mz means the higher moment of the higher molecular weight distribution based on the mathematical definition
3
∑n,m,"
∑n.m,' where n, is the number of molecules of molecular weight M,
Molecular Weight Measurement — The following equipment and procedures are used herein for the determination of molecular weight distributions of resins using gel permeation chromatography (GPC)
Equipment
Viscotek DG-700 Solvent Degasser Thermo Separation Products P1000 Pump Thermo Separation Products AS100 Autosampler
Polymer Labs PLgel 3 micron Mixed-E Column, 300 mm x 7.5 mm Viscotek T50A Viscometer Detector Viscotek LR40 Laser Refractometer Detector Gateway P5-90 Computer with Viscotek Trisec GPC Software version 3.0
Run Conditions:
Solvent: Tetrahydrofuran (THF)
Column temperature: 50°C Sample concentration (calibration standards): approximately 1 .75 mg/mL
Sample concentration (resin samples): approximately 5.25 mg/mL
Injection Volume: 100 microliters
Injections per sample: 2 Flow rate: 0.50 mL/min
Run time: 45 minutes per sample
Calibration:
The column is calibrated using polystyrene standards with peak molecular weights ranging from 162 to 19600. For each calibration standard, 35+/-1 mg of sample is dissolved in 20 mL of THF solvent. Aliquots of about 1.5 mL of each standard solution are loaded into the autosampler for analysis according to the run conditions shown above. The calibration is calculated using the Universal Calibration method. Molecular weight (Mn, Mw and Mz) are obtained from the Universal Calibration curve.
Aromatic Hydrogen Content — the aromatic hydrogen content is defined as the ratio of integration area of aromatic hydrogen relative to the total integration area of hydrogen on the resin's proton nuclear magnetic resonance (1H NMR) spectrum.
1H NMR analyses of the resins in this invention were performed using a JEOL 400 MHz Eclipse÷ NMR system with a pulse interval of 10 seconds, acquisition time of 2.7 seconds, pulse angle of 45°, X resolution of 0.37 Hz and number of scans of 200. The resin NMR samples are prepared by dissolving known amounts of resins into a carbon tetrachloride solvent containing 0.1 % V/V 1 ,4-dioxane as an internal standard. The carbon tetrachloride and 1 ,4-dioxane solvents are reagent grade and available from Aldrich Company. The aromatic and olefinic peak areas at approximately 7 ppm and at approximately 5.2 ppm, respectively, are integrated relative to the dioxane peak area at 3.53 ppm for comparative analysis.
Example 1
In this example, there is described the polymerization of 5-phenyl-2- norbornene, wherein the hydrocarbon resin was obtained in a high yield of about 76%, using a boron trifluoride catalyst.
To a nitrogen flushed, oven-dried, 500 mL, round-bottom 4-neck flask equipped with an overhead stirrer, thermometer, condenser and additional funnel was charged 120 g of 5-phenyl-2-norbornene, 30 g of toluene and 1 .8 g of boron trifluoride diethyl ether complex (BF3.Et2O, 1 ,8% by weight of monomer). The reaction mixture was stirred and heated to 115°C for 4 hours. At the end of 4 hours, the mixture was worked up by diluting with 1 50 mL of toluene. When the temperature dropped below 80°C, about 50 mL of 10% aqueous NaOH solution was added to neutralize the catalyst. The organic layer was separated from the mixture, dried, filtered and the volatile components were removed by heating under vacuum (10 mmHg) until the base temperature reached 271 °C. The yield of the resin was about 76%. The molten resin displayed a 13 color on the Gardner scale (neat) and a softening point of 70°C. A 1H NMR analysis
showed that this resin had 33% of aromatic hydrogens (calculated theoretical value was 35.7%).
Further, the homopolymer of the 5-phenyl-2-norbornene had a number average molecular weight (Mn) of 150, a weight average molecular weight (Mw) of 170, and a z-average molecular weight (Mz) of 190.
Example 2
In this example there is described the preparation of a homopolymer of 5-phenyl-2-norbomene, in a high yield of about 80%, using a boron trifluoride complex as catalyst.
Using the same setup and under the similar conditions described in Example 1 , 250 g of 5-phenyl-2-norbomene and 2.5 g (1 % by weight) of boron trifluoride phosphoric acid complex (BF3.H3PO4) were allowed to react at 130°C for 4 hours. At the end of 4 hours, the mixture was worked up by diluting with 150 mL of toluene. When the temperature dropped below 80°C, about 100 mL of 0% aqueous NaOH solution was added to neutralize the catalyst. The organic layer was separated from the mixture, dried, filtered and the volatile components were removed by heating under vacuum (10 mmHg) until the base temperature reached 271 °C. The yield of the resin was about 80%. The molten resin displayed an 18 color on the
Gardner scale and a softening point of 68°C. A 1H NMR analysis showed that this resin had 32.6% of aromatic hydrogens (calculated theoretical value was 35.7%). Further, the homopolymer of the 5-phenyl-2-norbornene had a number average molecular weight (Mn) of 150, a weight average molecular weight (Mw) of 190, and a z-average molecular weight (Mz) of
260.
Example 3
In this example, there is described the preparation of a homopolymer of 5-phenyl-2-norbomene, in a high yield of 66%, using an aluminum trichloride (AICI3) as catalyst. Using the same reaction set-up and conditions as in Example 1 , 100 g of 5-phenyl-2-norbomene, 25 g of mineral spirits and 0.5 g of aluminum chloride (0.5% by weight) were polymerized at 120°C for 4 hours. Then the mixture was worked up by diluting with 150 mL of toluene. When the temperature dropped below 80°C, about 50 mL of 10% aqueous NaOH solution was added to neutralize the catalyst. The organic layer was separated from the mixture, dried, filtered and the volatile components were removed by heating under vacuum (10 mmHg) until the base temperature reached 271 °C. The yield of the resin was 66%. The molten resin displayed a 15 color on the Gardner scale (neat) and a softening point of 95°C. A 1H NMR analysis showed that this resin had 33.1 % of aromatic hydrogens (calculated theoretical value was 35.7%). Further, the homopolymer of the 5-phenyl-2-norbornene had a number average molecular weight (Mn) of 190, a weight average molecular weight (Mw) of 450, and a z-average molecular weight (Mz) of 1590.
Example 4
In this example, there is described the preparation of an interpolymer of 5-phenyl-2-norbomene, styrene and THMINA (3a,4,7,7a-tetrahydro-4,7- methanoindan), in a high yield of about 81 %, using aluminum trichloride (AICI3) as catalyst.
To a nitrogen flushed, over-dried, 1 L round-bottom 4-neck flask equipped with an overhead stirrer, thermometer, condenser and additional funnel, was charged 150 g of 5-phenyl-2-norbomene, 50 g of mineral spirits and 2.8 g (0.8% by weight) of aluminum chloride. To the additional funnel was placed a premixed solution of 90 g of THMINA (3a,4,7,7a-tetrahydro-
4,7-methanoindan), 60 g of styrene and 50 g of mineral spirits. The addition of the mixture (THMINA-styrene) was begun when the reaction solution reached 1 15°C. The addition was controlled very slowly so that the addition process required about 60 minutes. The reaction was allowed to proceed for an additional 3.5 hours. When the reaction was finished, the mixture was worked up by diluting with 100 mL of toluene and 200 mL of mineral spirits. When the temperature dropped below 100°C, about 100 mL of 10% aqueous NaOH solution was added to neutralize the catalyst. The organic layer was separated from the mixture, dried, filtered and the volatile components were stripped under vacuum (20 mmHg) until the base temperature reached 290°C. The yield of the resin was about 81 %. The resin displayed an 18 color on the Gardner scale (neat) and a softening point of 99°C. H NMR analysis showed that this resin had 23% of aromatic hydrogens. Further, the interpolymer of 5-phenyl-2-norbomene, styrene and THMINA had a number average molecular weight (M„) of 340, a weight average molecular weight (Mw) of 860, and a z-average molecular weight (Mz) of 3200.
Examples 5 and 6 In the following Examples 5 and 6, there is described the preparation of novel hydrogenated hydrocarbon resins. The novel hydrogenated hydrocarbon resins were prepared by hydrogenating the novel homopolymer of 5-phenyl-2-norbomene of Example 2, and by hydrogenating the novel interpolymer comprising 5-phenyl-2-norbornene, styrene and THMINA, of Example 4. The hydrocarbon resins of Examples
2 and 4 were hydrogenated using a palladium (Pd) catalyst comprising 1 % Pd on alumina, available from Engelhard, under a reaction pressure of 1000 psig of hydrogen.
Example 5
In this example, there is described the preparation of a novel hydrogenated homopolymer of 5-phenyl-2-norbornene
The 5-phenyl-2-norbomene homopolymer of Example 2 was used herein (referred to as resin) 500 g of a solution of the resin (in xylenes,
30% solids) and 18 g of Pd catalyst (1 % Pd on alumina, available from Engelhard, S-95-618) were placed into a 2-lιter autoclave The hydrogenation was conducted at 1000 psig of H2, 280°C and held for 4 hours At the end of the reaction, the solution was dried, filtered and the solvent was removed by stripping at 290°C/20mmHg Hydrogenated resin was obtained in 97% yield and the resin displayed a 7 color on the Gardner scale (neat) and a softening point of 70°C
Example 6 In this example, there is described the preparation of a novel hydrogenated interpolymer comprised of 50% 5-phenyl-2-norbomene, 20% styrene and 30% THMINA, the resin produced in Example 4 (referred to as resin herein)
566 g of a solution of the resin (in mineral spirits, 36.5% solids) was treated with 25 g of alumina (obtained from LaRoche, A-2) at 250°C for two hours in order to remove organic chlorides Then the solution was dried and filtered 492 g of the treated resin solution and 18 g of Pd catalyst (1 % Pd on alumina, obtained from Engelhard, S-95-618) were placed into a 2- liter autoclave The hydrogenation was conducted at 1000 psig of H2, 250°C and held for 4 hours At the end of the reaction, the solution was dried, filtered and the solvent was removed by stripping under vacuum (20 mmHg) until the base temperature reached 290°C Hydrogenated resin was obtained in 98% yield and it displayed a 9.5 color on the Gardner scale (neat) and a softening point of 105°C. 1H NMR showed aromatic hydrogen content of this resin was about 19% Average number molecular weight
Mn) was 350. Average weight molecular weight (Mw) was 810. The z- average weight molecular weight (Mz) was 2600. This resin had a cloud point of DACP 7.9°C and MMAP 24.2°C. These cloud point data indicate this resin would be useful as a tackifying resin in many adhesive formulations
The 5-aryl-2-norbornene homopolymers and interpolymers of this invention, and the hydrogenated 5-aryl-2-norbomene homopolymers and interpolymers of this invention have good properties with regard to compatibility and solubility and can be used effectively as tackifying resins in coatings and adhesives formulations including, but not limited to, non- woven, SBS, acrylics, SIS, and many other applications. The resins can also be used in sealants, paints, labels, tapes, modifiers, extenders and processing aids for plastics, printing inks, overprint varnishes and other clear coatings, textile dry sizes, ceramic tile grout, varnishes, waterproofing compositions and wax compounds.
Example 7
In a manner similar to Example 1 there are prepared homopolymers of 3-methyl-phenyl-2-norbomene and 4-methyl-phenyl-2-norbomene.
Example 8
In a manner similar to Example 4, there is prepared an interpolymer of 5-phenyl-2-norbomene with 1 ,5-cyclooctadiene.
It should be clearly understood that the forms of the invention herein described are illustrative only and are not intended to limit the scope of the invention. The present invention includes all modifications falling within the scope of the following claims.
Claims
1 . A homopolymer of 5-aryl-2-norbomene, wherein the aryl is an aromatic group having at least 5 carbon atoms, said homopolymer characterized by having (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z- average molecular weight (Mz) ranging from about 150 to 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen.
2. The homopolymer according to Claim 1 wherein the aromatic group is selected from the group consisting of phenyl, substituted phenyl, indenyl, substituted indenyl, naphthyl and substituted naphtyl.
3. The homopolymer according to Claim 2 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl.
4. The homopolymer according to Claim 3 wherein the aromatic group is phenyl.
5. An interpolymer comprising a 5-aryl-2-norbornene, and at least one, or more, other cyclic or acyclic alkene, wherein the aryl of the 5-aryl- 2-norbornene is an aromatic group having at least 5 carbon atoms, wherein the alkene has from about 3 to about 20 carbon atoms, and wherein said interpolymer is characterized by having a softening
point ranging from about 50°C to about 150X, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z-average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen.
6. The interpolymer according to Claim 5 wherein the aromatic group is selected from the group consisting of phenyl, substituted phenyl, indenyl, substituted indenyl, naphthyl and substituted naphthyl.
7. The interpolymer according to Claim 6 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl.
8. The interpolymer according to Claim 7 wherein the aromatic group is phenyl.
9. The interpolymer according to Claim 5 wherein the at least one, or more cyclic or acyclic alkene is selected from the group consisting of cyclopentene, dicyclopentadiene, 1 ,5-dicyclooctadiene, 3a,4,7,7a- tetrahydro-4,7-methanoindan, 5,6-dihydrodicyclopentadiene, pentenes, piperylene, styrene, alpha-methylstyrene, indene and vinyltoluene.
10. The interpolymer according to Claim 5 wherein the aryl is phenyl, and wherein the alkenes are styrene and 3a,4,7,7a-tetrahydro-4,7- methanoindan.
1 . A process for preparing a homopolymer of 5-aryl-2-norbornene wherein the aryl is an aromatic group having at least 5 carbon atoms, said homopolymer characterized by having (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z-average molecular weight (Mz) ranging from about 150 to 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen, said process comprising polymerizing, under polymerization conditions, a
5-aryl-2-norbornene wherein the aryl is an aromatic group having at least 5 carbon atoms in the presence of a Friedel-Crafts catalyst.
12. The process according to Claim 1 1 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl.
13. The process according to Claim 1 1 wherein the Friedel-Crafts catalyst is selected from the group consisting of a metal halide, a boron halide and a strong acid.
14. The process according to Claim 13 wherein the metal halide is aluminum trichloride and the boron halide is boron trifluoride.
15. A process for preparing an interpolymer comprising a 5-aryl-2- norbornene and at least one, or more, other cyclic or acyclic alkene, wherein the aryl of the 5-aryl-2-norbornene is an aromatic group having at least 5 carbon atoms, wherein the alkene has from about 3 to about 20 carbon atoms, and wherein said interpolymer is characterized by having (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn)
ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z- average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen, said process comprising polymerizing a 5-aryl-2-norbomene wherein the aryl of the 5-aryl-2-norbornene is an aromatic group having at least 5 carbon atoms, and at least one, or more, other cyclic or acyclic alkene having from about 3 to about 20 carbon atoms, under polymerization conditions, in the presence of a Friedel-Crafts catalyst.
16. The process according to Claim 15 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl.
17. The process according to Claim 15 wherein the Friedel-Crafts catalyst is selected from the group consisting of a metal halide, a boron halide and a strong acid.
18. The process according to Claim 17 wherein the metal halide is aluminum trichloride and the boron halide is boron trifluoride.
19. The process according to Claim 15 wherein the at least one, or more, cyclic or acyclic alkene is selected from the group consisting of cyclopentene, dicyclopentadiene, 1 ,5-dicyclooctadiene, 3a,4,7,7a- tetrahydro-4,7-methanoindan, 5,6-dihydrodicyclopentadiene, pentenes, piperylene, styrene, alpha-methylstyrene, indene and vinyltoluene.
0. The process according to Claim 19 wherein the aryl is phenyl, and wherein the alkenes are styrene and 3a,4,7,7a-tetrahydro-4,7- methanoindan.
1 . A hydrogenated homopolymer of 5-aryl-2-norbornene, wherein the aryl is an aromatic group having at least 5 carbon atoms, said hydrogenated homopolymer characterized by having (a) a softening point ranging from about 50°C to about 1 50°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z-average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen.
22. The hydrogenated homopolymer according to Claim 21 wherein the aromatic group is selected from the group consisting of phenyl, substituted phenyl, indenyl, substituted indenyl, naphthyl and substituted naphthyl.
23. The hydrogenated homopolymer according to Claim 22 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl.
24. The hydrogenated homopolymer according to Claim 23 wherein the aromatic group is phenyl.
25. A hydrogenated interpolymer comprising a hydrogenated interpolymer comprised of a 5-aryl-2-norbornene, and at least one, or more, other cyclic or acyclic alkene, wherein the aryl of the 5-aryl-2-
norbornene is an aromatic group having at least 5 carbon atoms, wherein the alkene has from about 3 to about 20 carbon atoms, and wherein said hydrogenated interpolymer is characterized by having (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z-average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen.
26. The hydrogenated interpolymer according to Claim 25 wherein the aromatic group is selected from the group consisting of phenyl, substituted phenyl, indenyl, substituted indenyl, naphthyl and substituted naphthyl.
27. The hydrogenated interpolymer according to Claim 26 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl.
28. The hydrogenated interpolymer according to Claim 25 wherein the at least one, or more, cyclic or acyclic alkene is selected from the group consisting of cyclopentene, dicyclopentadiene, 1 ,5-dicyclooctadiene, 3a,4,7,7a-tetrahydro-4,7-methanoindan, 5,6- dihydrodicyclopentadiene, pentenes, piperylene, styrene, alpha- methylstyrene, indene and vinyltoluene.
29. The hydrogenated interpolymer according to Claim 25 wherein the aryl is phenyl, and wherein the alkenes are styrene and 3a,4,7,7a- tetrahydro-4,7-methanoindan.
A tackifier composition comprising a homopolymer of 5-aryl-2- norbornene, wherein the aryl is an aromatic group having at least 5 carbon atoms, said homopolymer characterized by having (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 to about 2000, (d) a z-average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen
The tackifier composition according to Claim 30 wherein the aromatic group of the homopolymer is selected from the group consisting of phenyl, substituted phenyl, indenyl, substituted indenyl, naphthyl and substituted naphthyl
The tackifier composition according to Claim 31 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl
A tackifier composition comprising an interpolymer comprising a 5- aryl-2-norbomene and at least one, or more, other cyclic or acyclic alkene, wherein the aryl of the 5-aryl-2-norbornene is an aromatic group having at least 5 carbon atoms, wherein the alkene has from about 3 to about 20 carbon atoms, and wherein said interpolymer is characterized by having (a) a softening point ranging from about 50°C to about 150°C, (b) a number average molecular weight (Mn) ranging from about 120 to about 1000, (c) a weight average molecular weight (Mw) ranging from about 150 'to about 2000, (d ) a z-
average molecular weight (Mz) ranging from about 150 to about 4000, and (e) a level of aromatic hydrogen ranging from about 8% to about 40% with respect to the total hydrogen
The tackifier composition according to Claim 33 wherein the aromatic group of the interpolymer is selected from the group consisting of phenyl, substituted phenyl, indenyl, substituted indenyl, naphthyl and substituted naphthyl
The tackifier composition according to Claim 34 wherein the aromatic group is selected from the group consisting of phenyl and substituted phenyl
The tackifier composition according to Claim 33 wherein the at least one, or more cyclic or acyclic alkene of the interpolymer is selected from the group consisting of cyclopentene, dicyclopentadiene, 1 ,5- dicyclooctadiene 3a,4,7,7a-tetrahydro-4,7-methanoιndan, 5,6- dihydrodicyclopentadiene, pentenes, piperylene, styrene, alpha- methylstyrene, indene and vinyltoluene
The tackifier composition according to Claim 33 wherein the aryl is phenyl, and wherein the alkenes are styrene and 3a,4,7,7a- tetrahydro-4,7-methanoιndan
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US957379 | 2001-09-20 | ||
US09/957,379 US6429272B1 (en) | 2001-09-20 | 2001-09-20 | Hydrocarbon resins from aryl norbornene derivatives |
PCT/US2002/028532 WO2003025030A1 (en) | 2001-09-20 | 2002-09-06 | Hydrocarbon resins from aryl norbornene derivatives |
Publications (1)
Publication Number | Publication Date |
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EP1427764A1 true EP1427764A1 (en) | 2004-06-16 |
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ID=25499495
Family Applications (1)
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EP02766258A Withdrawn EP1427764A1 (en) | 2001-09-20 | 2002-09-06 | Hydrocarbon resins from aryl norbornene derivatives |
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US (1) | US6429272B1 (en) |
EP (1) | EP1427764A1 (en) |
JP (1) | JP2005503458A (en) |
BR (1) | BR0211420A (en) |
MX (1) | MXPA04002486A (en) |
WO (1) | WO2003025030A1 (en) |
Families Citing this family (3)
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EP1435350A4 (en) * | 2001-10-10 | 2006-02-08 | Jsr Corp | Norbornene derivative and norbornene polymer obtained therefrom through ring-opening polymerization |
JP2008007537A (en) * | 2006-06-27 | 2008-01-17 | Idemitsu Kosan Co Ltd | Manufacturing method of aromatic compound containing alicyclic substituent and low dielectric material |
US7550546B2 (en) * | 2006-07-28 | 2009-06-23 | Fujifilm Corporation | Norbornene-based polymers, films, polarizing plates and liquid crystal display devices |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2721189A (en) | 1954-08-30 | 1955-10-18 | Du Pont | Polymeric bicyclo-(2, 2, 1)-2-heptene |
US3494897A (en) * | 1963-12-05 | 1970-02-10 | Union Carbide Corp | Ethylene/bicyclo(2.2.1)hept-2-ene copolymers |
US3330815A (en) | 1964-03-24 | 1967-07-11 | Union Carbide Corp | Novel polynorbornenes, process for production thereof, and products produced therefrom |
US4342850A (en) | 1980-10-27 | 1982-08-03 | Eastman Kodak Company | Process for the preparation of hydrocarbon resins |
US4393261A (en) | 1982-09-22 | 1983-07-12 | Eastman Kodak Company | Hydrocarbon resin and process for preparation |
US4801668A (en) | 1987-07-06 | 1989-01-31 | Eastman Kodak Company | High softening point hydrocarbon resins from 1,5-cyclooctadiene |
JPH0751609B2 (en) * | 1988-01-20 | 1995-06-05 | 日本石油株式会社 | Random copolymer and method for producing the same |
US5629398A (en) * | 1990-10-05 | 1997-05-13 | Idemitsu Kosan Co., Ltd. | Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers |
CA2061003C (en) * | 1991-02-12 | 1999-02-09 | Mitsui Chemicals, Inc. | Process for isomerizing endo-form of aromatic group-containing norbornenes to exo-form thereof, isomer mixture of aromatic group-containing norbornenes and process for preparing same, and ethylene/aromatic group-contain ng norbornene copolymer and process for preparing same |
US5656698A (en) | 1993-11-03 | 1997-08-12 | Exxon Chemical Patents Inc. | Aromatic tackifier resin |
FI105196B (en) | 1995-05-08 | 2000-06-30 | Optatech Oy | Amorphous olefin co / terpolymers |
US5677405A (en) * | 1995-05-24 | 1997-10-14 | The B.F. Goodrich Company | Homopolymers and copolymers of cationically polymerizable monomers and method of their preparation |
EP0871675B1 (en) * | 1995-12-07 | 2002-10-30 | ExxonMobil Chemical Patents Inc. | Tackifiers and a process to obtain tackifiers |
EP1205497A3 (en) * | 2000-11-10 | 2002-06-12 | Maruzen Petrochemical Co., Ltd. | Method for producing an olefin type copolymer having a cyclic structure |
-
2001
- 2001-09-20 US US09/957,379 patent/US6429272B1/en not_active Expired - Fee Related
-
2002
- 2002-09-06 MX MXPA04002486A patent/MXPA04002486A/en not_active Application Discontinuation
- 2002-09-06 BR BR0211420-8A patent/BR0211420A/en not_active Application Discontinuation
- 2002-09-06 WO PCT/US2002/028532 patent/WO2003025030A1/en active Application Filing
- 2002-09-06 JP JP2003528874A patent/JP2005503458A/en active Pending
- 2002-09-06 EP EP02766258A patent/EP1427764A1/en not_active Withdrawn
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JP2005503458A (en) | 2005-02-03 |
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